Process for producing anhydrous alcohol



March'18, 1930. o. LEONORI 1,7515211 v PROCESS FOR PRODUCING ANHYDROUS ALCOHOL Filgd June 9. '1927 which is costly and difficult.

Patented Mar. 18, 1930 UNITED -sTATEs PATENT 'OFFICE OVTDIQ LEONOR/I, 0F NARNI, ITALY PROCESS FOR PRODUCING ANHYDROUS ALOHOL Application led June 9, 1927, Serial No. 197,769, and in'Italy June 26, 126.

The present invention concerns an industrially practicable process for obtaining the complete dehydration of alcohol, when'the latter is to be mixed in a stable and perfect manner with benzine, petrol, heavy oil, liquid and solid hydrocarbons of the eliphatic and aromatic series, both for forming carbureting mixtures, such as are used in internal combustionI engines and for producing solvents of resins, lacs, cellulose, guttapercha,

rubber and similar substances.

The new process is such that the dehydrated alcohol obtained thereby isnot only completely anhydrous, but is further enriched with synthetic products which remain dissolved in it durin the treatment and which increase its calori c power adding to it other desirable qualities.

The process consists substantially in the preliminary treatment of alcohol containing water with gaseous ammonia, till the complete saturation of the water is obtained, and in then letting react on said water a mixture of carbides and hydridescapable of being decomposed in the .water in such quantity as to bind all the water present, then 'separating the anhydrous alcohol from the precipitate by decanting and finally clarifying by means of a weak electric current which liberates the liquid from all the extremel attenuated solid particles suspended therein and rendering it turbid. The aforesaid operations are all carried out so as not to cause any loss of the materials'employed, While all the products of the reactions are recovered.

In practicey the process is carried out in the' following'manner, the annexed drawing showing diagrammat-ically, by way of example, a sectional view of a devlce for affecting the dehydration of alcohol according to my invention.

The usual commercial alcohol containing from about 5% to 26% of water, is treated with gaseous ammonia so as to completely 50 saturate, at the normal temperature,fthe wa- 4ter which it contains. For this treatment gaseous ammonia is employed instead of ammonia in solution so as not to increase the quantity of water contained in the alcohol. Then, the alcohol, saturated with ammonia, is. placed in contact with a mixture, in due proportions, of carbide of calcium and other carbides decomposable in water, such as, for

example, the carbides of aluminum, barium,

manganese, sodium etc. to which carbides may be added a small quantity of hydrides of aluminum and calcium.

The treatment with carbide. of calcium alone is old, but the addition of other carbides and of the aforesaid hydrides will produce effects unobtainable by the use of carbide of calciumalone. In fact, some carbides, e. g. carbide of aluminum, have a peculiar coagulating and purifying action of their-- own; other carbides, e. g. carbide of manganese, cause the formation of synthetic products both in the decomposition of the carbide itself and through the action of various gases in the nascentstate which develop from the reaction. For instance, the object of the addition of the hydrides of calcium and of aluminum is the production of hydrogen in the nascent state.

Coming in contact with the water contained in the alcohol, the said carbides and hydrides are decomposed, forming different gases, such as acetylene, ethylene, methane and hydrogen, which act on the liquid in the nascent state.

In the first place', there is a dehydrating and coagulating action, due to the formation of hydroxides of calcium, aluminum etc., and at the same time a catalytic action exerted by the metallic carbides on the nascent gases, acetylene, ethylene, methane and hydrogen thus enriching the alcohol with liquid products of a high calorific power, whichimprove its ualities as a fuel; on the other hand, the solu ility of the acetylene in the alcohol is diminished, so that it is dissolved in the liquid in not excessive quantities. Moreover, its presence tends to diminish the hygroscopicity of anhydrous alcohol.l L

The above described reaction takes place rapidly at the ordinary temperature, but it may be hastened by a slight heating of the alcohol to a temperature between 30 and 40 degrees contigrade.

For this purpose it is advisible to make use of a closed cylindrical vessel shown at 1 in the drawing, having a conical bottom 2 and double walls 3, 3 so as to allow the circulation of hot water or steam. On the conical bottom is placed a basket 4 of perforated plate or a metal net containing the mixture of carbides and hydrides as aforesaid. The heating lapparatus has two opening, 5, (i for the inlet and the `outlet of the steam; the conical bottom has a discharge opening 7 in order to free the cylinder from the accumulating deposit; the said cylinder is provided with three or more discharge cocks at Various heights, one cock being shown at 8 for the purpose of decanting the alcohol above the deposit, and moreover has a little glass window 9 in its side in order to observe the level of the muddy deposit. The cylinder is closed.

on the top by a movable lid 10, which is taken off to introduce or remove the basket. The lid has an opening 11 adapted to be closed by a screw stopper 12 to introduce the mixture of carbides and hydrides. A flmnel 13 is provided in the lid'for the introduction ofthe alcohol and a tube 14 for the lescape of the vacetylene and the other gases which are formed, and which, after 'rst passing through a refrigerating apparatus where the alcohol vapours are condensed and through a common washing apparatus where they are deprived of their ammonia, reach a meter from which they are collected in the bell of a asometer. The lid of the rece tacle is also garnished with another tube 15 or the escape otlcohol vapours, as will .be explained herea r.

The bcomplete dehydration is accomplished in about half an liour, and the presence of the ammonia saturating the water contained .in the alcohol has the eii'ect of eliminating those substances, such as sulphurated hydrogen, lphosphorated hydrogen and the like, which are developed in the reaction by reason of the impurities contained in the carbides used, and which lwould inquinate the gases arising from the reaction. The am; monia has also the action of facilitating the disinte ration of the deposits consisting of p finely s redded metallic hydrates.

In order to obtain the complete separation of these hydrates and consequently a complete limpidity, the alcohol, after being rendered anhydrous and enriched is decanted through one of the .cocks provided in the side of the cylinder and is poured into l'areceptacle for its clarification, wherein, as a' further precaution, is placed another basket with the same mixture of carbides as contained in thedehydration recipient, so as to thoroughly ensure the elimination of any trace of water; into this clarifying vessel are lintroduced small quantities of alcohol de- A rived from the condensation of the vapours carried away by thegases of the reaction.

The residuum' in the dehydrating vessel still contains a considerable quantity of anhydrous alcohol. In order to recover it, after the decanting of the overlying liquid, steam is introduced through. the tubes 16 i and 17 into the lower 4portions of the heating and with that derived from the condensation of the vapours which escaped together with the reaction gases.

Anhydrous alcohol thus collected in the clarifying vessel is always slightly turbid, because it still contains very small' particles of metallic hydroxides in a state of suspension which do not deposit, norcan be separated by ordinary filtering or by means of pressure. Itv is possible, however, to eliminate them rapidly and to render the liquid' mass perfectly limpi-d, by havin@r recourse to precipitation. It is suicient for the purpose to dip into the liquid two electrodes communicating with the opposite poles of .a battery of a few elements, and in a few minutes a complete clarification is obtained, all the particles depositing on the cathode.

The alcohol, perfectly limpid, thus 4ob. tained, is absolutely anhydrous, and may be mixed with benzine, benzol, hydronaphthalenev and other hydrocarbons of the eliphatic or aromatic series, light or heavy according to the use 4for which it is meant; and the alcohol has the characteristics required, either as fuel for internal combustion motors or as a solvent for'resins, lacs, cellulosic ethers, rubber, etc.

, The above described process may be acl-- vantageously applied inorder to render perfectly anhydrous all alcoholsof the fattyy series, and moresespecially methylic alcohol, ethylic, propylic, butilic, amilic, etc., however obtained. 'lhe said vprocess further permits the recovery and utilization of all the materials employed therein, such' as ammonia, acetylene and other gases, hydrates, etc., so that the sale of the by-products covers the cost of the dehydration ofthe alcohol.

vI claim: 1

1. The process of producing anhydrou alcohol to be used principally in the preparation .of fuels andsolvents, which consists intreating aqueous alcohol with a mixture and hydrides of calcium and aluminum.

2. The process of producing arhydrous alcohol as specified in claim 1, in which, as a preliminary step, the water contained in the alcohol is saturated with aseous ammonia.

3. The process of pro ucing anhydrous alcohol as specified in claim'l, in which as a preliminary step, the Water contained in the alcohol is saturated with aseous ammonia, and the acetylene and ot 'er gases formed by the reaction, are collected after assing through a washing apparatus for t e purpose of recovering by condensation the vapours of alcohol escaping together with said gases.

4. The process of producing anhydrous alcohol which consists in causing the aqueous alcohol, the water of which is saturated with gaseous ammonia, to react with a mixture of metallic carbides decomposable by water,

and hydrides of calcium and aluminum, and i finally heatinafter the decantng of the dehydrated alco ol, the residuar deposit for distilling therefrom the alco ol which it contains, and passing the vapours of said alcohol through alayer of carbides.

In testimony whereof I have aiiixed my si gnature at Rome this 25th day of May, 1927.

OVIDIO LEONORL 

